Application Note
Environmental
Authors
Gaël Monvoisin, CNRS, Orsay
University, France and
Marion Legall, LSCE, CNRS,
CEA, Gif sur Yvette
Maud Costedoat,
Agilent Technologies France
Photo by: M.C. Gromaire Mertz
Determination of Sb in Sediment and
Road Soil
Using the Agilent 240 Zeeman graphite furnace
atomic absorption spectrometer
Introduction
Antimony (Sb) is widely used as a flame-retardant in the textiles and plastics
industries. It is also used as a paint pigment, and ceramic opacifier or catalyst. Its
wide use means that it can find its way into the environment as a pollutant. Its main
anthropogenic sources include smelting activities, emissions from vehicle brake
pads, waste disposal or incineration, and shooting activities.
Recognized as potentially harmful at very low concentrations and listed by the US
Environmental Protection Agency as a ‘priority pollutant’, antimony sources and
pathways to the environment are the subject of investigation by researchers and
regulators.
Soils or sediments are likely to hold Sb. They are complex matrices to analyze,
requiring the development of a reliable analytical method for the determination of
antimony at low levels. Graphite furnace atomic absorption spectrometry offers
suitable sensitivity at a lower cost than ICP-MS for this analysis.
This study describes the method and performance of Table 1. Instrument Settings. Sample collection and preparation In the furnace program, the ash and atomize temperatures
the Agilent 240Z graphite furnace atomic absorption 10 L of river waters were filtered at < 0.45 µm porosity to were rounded to 925 and 2200 °C respectively.
spectrometer when measuring Sb at very low concentrations Instrument Parameter Setting
collect the particulate phase of water: Suspended Particulate
in environmental samples. Results were compared to those Wavelength 217.6 nm Matters (Sample 1).
obtained using an ICP-MS instrument. Slit 0.2 nm
Integrative samples collected during four to five days by
Lamp current 10 mA
Experimental Background correction Zeeman
sediment traps to get long term Suspended Particulate
Matters. Then centrifuged (375 g) and freeze-dried. Sediments
Instrumentation Replicates 3
were dried and sieved at 2 mm (Sample 2).
Calibration mode Standard additions
Furnace measurements were performed using an Agilent Road soil samples specific from urban areas, called Road
Sample volume 20 µL
240Z AA spectrometer with transverse Zeeman background Deposited Sediments (RDS), were sampled in the gutter of a
correction. The instrument features the highly sensitive and Modifier volume 5 µL
street (Samples 3 and 4). The RDS were dried and sieved at
accurate Agilent GTA 120 Graphite Tube Atomizer (GTA) and Modifier injection type Co-injection
200 µm to keep the contaminants bound to finer fraction and
an Agilent PSD 120 Programmable Sample Dispenser (PSD) Total volume 30 µL
discard gravels.
autosampler, as shown in Figure 1. The PSD automatically Hot injection temperature 60 °C
All sediments and RDS were ground in an agate mortar.
delivers measured volumes of the sample to the furnace. The Injection speed 3
Approximately 100 mg of SPM was mineralized in PTFE
Agilent PSD 120 provides the capacity for up to 135 solutions
beakers and heated by DigiPREP block under an exhaust
and performs automatic standard preparation, modifier
hood. A three-phase-digestion was performed. First, 4 mL
addition, and overrange dilution. Table 2. Furnace Settings.
of HF (30 %) and 2 mL HClO4 (67 %) were left at ambient
Step Temp (ºC) Time (s) Argon Flow (L/min) Read temperature for 2 hours then heated at 150 °C for 6 hours.
1 80 60 0.3
The second digestion phase saw the addition of 3.75 mL of
HCl (30 %) and 1.25 mL of HNO3 (67 %). The solution was
2 120 30 0.3 Figure 2. SRM ash and atomization optimization.
then kept at ambient temperature for 8 hours before heating
3 925 20 0.3
at 120 °C during 3 hours and 20 minutes. Finally, three
4 925 10 0.3
successive evaporations of 1 hour at 110 °C after addition
5 925 1 0
of 1 mL of HNO3 (67 %) were performed. The dry evaporated Calibration
6 2200 0.6 0 Yes Standard addition calibration graphs are shown for each
residue was then redissolved in 50 mL of HNO3 at 2 % v/v.
7 2200 2 0 Yes sample in Figure 3. Excellent correlation coefficients were
8 2600 2 0.2 Results and discussion obtained as shown in Table 4.
Figure 1. Agilent PSD-120 programmable sample dispenser. 9 40 21.5 0.3
Optimization
The Agilent 240Z instrument features a furnace viewing
The 240Z AA comprises patented longitudinal graphite tube camera, Tube-CAM. This provided real time viewing inside the
Reagents graphite Omega tube and was used to optimize drying steps.
heating and a Constant Temperature Zone (CTZ) design.
In addition to prolonging the graphite tube lifetime, these The following reagents were used for preparation of Ash and atomization temperatures were optimized using
features provide consistent, uniform heating, which is calibration solutions and for sample preparation: SRM (Surface Response Methodology) Wizard, within the
essential for the accurate low-level determination of complex • Antimony standard solution, 1000 mg/L instrument software. By choosing initial ash and atomize
samples. temperatures and steps for each (Table 3), the software
• High-purity HCl, HNO3, HClO4, HF automatically derived the experiments needed.
Atomization for antimony was from a pyrolytic platform • Class 1 Water (18 MΩ/cm)
Omega tube. The inert gas used was 99.99 % pure argon.
• 0.1 % palladium nitrate, Agilent partnumber: 5190-8335
Table 1 lists the instrument settings and Table 2 lists the Table 3. SRM Parameters.
furnace settings used in the analysis. • 1 % magnesium nitrate, Agilent partnumber: 5190-8338
The PSD 120 autosampler rinse solution was 2 % v/v of high Step Target Temperature (°C) Step (°C)
Figure 3. Standard addition calibrations on sample 1 to 4.
purity nitric acid. Ash 1000 200
Atomization 2100 200
1 g/L Mg(NO3)2, 6H2O + 0.9 g/L Pd(NO3)2 mixed modifier was
prepared.
Standards additions were prepared by the autosampler for Figure 2 shows the 3D shape and the optimum temperatures :
each sample with different volumes of a master standard
• Ash temperature: 932 °C
of 200 μg/L. Spiked concentrations are 10, 20, 40 µg/L. The
automixing capabilities of the sampler were utilized. • Atomization temperature: 2195 °C

2 3
Table 4. Slopes and correlation coefficients. Accuracy Characteristic Mass
To check accuracy, digested soil samples were first analyzed The Characteristic Mass (m0) expressed as the absolute
Sample Slope Correlation coefficient
once using ICP-MS. As shown in Table 6, recovery results mass of analyte giving a peak area of 0.0044 absorbance was
1 0.00337 0.9992
using this method were within ±10 % of the results obtained 24 pg for Antimony.
2 0.00332 0.9996
by ICP-MS.
3 0.00343 0.9995 Conclusions
4 0.00341 0.9990 The method using the Agilent 240Z graphite furnace AA
As shown in Table 4, the slope of the four samples is Table 6. ICP-MS comparison. provided accurate results for the determination of low levels
similar. That means that all samples had a similar signal (ppm) of antimony in soils and sediments. The results
Sample Analysis 1 Analysis 2 Analysis 3 Mean Std dev %
response. Therefore, instead of running standard additions obtained were within ±10 % of the results obtained on an ICP-
1 2.40 2.20 2.17 2.257 0.125 5.5 MS instrument.
on each sample, standard additions were performed on the
2 4.05 3.96 3.90 3.970 0.075 1.9
first sample only. More samples could thus be measured The instrument’s transverse Zeeman background correction
3 7.38 6.93 7.32 7.210 0.244 3.4
according to the first sample calibration. and the chemical modifier, Omega tube design, and
4 20.3 20.81 18.83 19.980 1.028 5.1
Figure 4 shows Sb peak profiles of three replicates of Sample temperature optimization by Surface Response Methodology
4 (low peaks) and one standard addition (high peaks). These allowed the development of a robust method. This meant
Long term stability single standard addition calibration was possible, saving time
overlays signals show the benefit of the platform in delaying
atomization of Antimony as described by the work done by Long term stability was tested by analyzing a sample over and reducing gas costs.
Boris L'Vov in 1978 (4) and by Walter Slavin et al in 1981 (5) in 50 times during more than 6 hours. The 240Z AA showed
the Stabilized Temperature Platform Furnace (STPF) concept. excellent stability over the 6 hour run with RSD values of less References
than 3.5 %. 1. H. Niskavaara, J. Virtasalo and L.H.J. Lajune,
Figure 5 shows that conditions remain stable during the Determination of antimony in geochemical samples by
6-hour sequence. graphite furnace atomic absorption spectrometry using
different matrix modifiers. Spectrochimica acta, 1985,
40B-9, 1219 – 1225.
2. R.G.O. Araujo, B. Welz, I.N.B. Castilho, M.G.R. Vale,
P. Smichowski, S.L.C Ferreira, H. Becker-Ross.
Determination of antimony in airborne particulate matter
collected on filters using direct solid sampling high-
resolution continuum source graphite furnace atomic
absorption spectrometry, J Anal At Spectrom., 2010, 25,
580–584.
Figure 4. Sb furnace signal on sample 4 and 40 µg/L standard addition. Figure 5. Sample stability over 6.5 hours 3. A.. Barros, D. Victor de Babos, E.C. Ferreira, J.A. Gomes
Neto, Effect of different precursors on generation of
Detection and quantification limits reference spectra for structural molecular background
Repeatability The detection and quantification limit expressed as the correction by solid sampling high-resolution continuum
To check repeatability, the four digested soil samples concentration equal to three and 10 (respectively) times the source graphite furnace atomic absorption spectrometry:
were analyzed three times. Table 5 shows measured standard deviation of the 10 concentration measurements Determination of antimony in cosmetics. Talanta, 2016,
concentrations results of the four samples, mean of a blank are shown in table 7. LOD and LOQ in mg/kg have 161, 547 – 553.
concentration and %RSD. been calculated based on sample preparation (100 mg weight 4. B.V, L'Vov. Electrothermal Atomization - The way towards
in 50 mL volume). absolute methods of atomic absorption analysis,
Spectrochimica acta, 1978, 33B, 153 - 193.
Table 5. Repeatability results.
Table 7. Detection and quantification limits. 5. W. Slavin and Al. The stabilized temperature platform
Sample Analysis 1 Analysis 2 Analysis 3 Mean Std dev C.V. furnace (STPF) concept, Atomic Spectrometry,1981
% In solution In soil
1 2.4 2.2 2.17 2.257 0.125 5.5 µg/L mg/kg

2 4.05 3.96 3.9 3.970 0.075 1.9 LOD 1 0.5

3 7.38 6.93 7.32 7.210 0.244 3.4 LOQ 2.9 1.4

4 20.3 20.81 18.83 19.980 1.028 5.1

4 5
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